Alkali Metals

Group 1 elements: lithium, sodium, potassium, rubidium, caesium, and francium Called alkali metals because their hydroxides are alkaline in nature

Electronic Configuration

General outer electronic configuration is ns1. The electronic configurations of the alkali metals are given in the following table. Element Lithium (Li) Sodium (Na) Potassium (K) Electronic configuration 1s2 2s1 1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p6 4s1

Rubidium (Rb) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s1 Caesium (Cs) Francium (Fr) Atomic and Ionic Radii

[Xe] 6s1 [Rn] 7s1

Increase with increase in atomic number (i.e., on moving down the group)

Ionization Enthalpy

Low Decreases on moving down the group, which is because of the following reasons: Increase in size Increase in screening of outermost electrons from the nuclear charge

Hydration Enthalpy

Decreases on moving down the group

Physical Properties

Silvery white, soft, and light metals Density increases down the group. (exception: Na is denser than K) Low melting and boiling points Reason: weak metallic bond due to the presence of only one electron in the outermost shell They and their salts impart characteristic colour to an oxidising flame. Reason: after getting heat from the flame, the valence electrons get excited to higher energy level. Then they come back to ground state by emitting radiation in the visible region. Chemical Properties

Highly reactive because of large size low ionization enthalpy Reactivity increases down the group. Reaction with air: Tarnish in dry air Reason: formation of oxides and then hydroxides with moisture Burn vigorously in air

Kept in kerosene oil Reason: highly reactive towards air and water Li reacts directly with nitrogen of air to form lithium nitride (Li3N). Reaction with water:

(M = alkali metal)

Reaction with dihydrogen:

Alkali metal hydrides are ionic solids with high melting point. Reaction with halogen: Reacts vigorously to form halides which are ionic in nature (exception: LiX is some what covalent Reason: High polarizing capability of Li+ ion) Li I is the most covalent. Reducing nature Strong reducing agent Li is the strongest and Na is the weakest. Solutions in liquid ammonia Dissolve in liquid ammonia to give conducting deep blue solution

Reason for blue colour The ammoniated electron absorbs energy in the visible region of light. The solution is paramagnetic in nature and liberates hydrogen to form amide.

(am stands for solution in ammonia)

Its concentrated solution is bronze in colour and diamagnetic in nature. Also reacts with alcohol, gaseous ammonia, and alkynes

Uses

In making useful alloys Li in making white metal bearings for motor engines Li is used in making electrochemical cells.

Na is used in making Na/Pb alloy, which are used to make organolead compounds PbEt4 and PbMe4. These compounds were earlier used as anti-knock additives to petrol. Liquid Na is used as a coolant in fast breeder nuclear reactors. K in biological system: KCl as a fertilizer KOH in the manufacture of soft soap, as an excellent absorbent of CO2 Cs is used in devising photoelectric cells.

Oxides and Hydroxides of Alkali Metals

Alkali metals form oxides on combustion. Li Lithium oxide (Li2O) (and some lithium peroxide Li2O2) Na Sodium peroxide (Na2O2) (and some sodium superoxide NaO2) K, Rb, Cs Superoxides, MO2 The stability of peroxides or superoxides increases on moving down the group (i.e., with increase in size). Reasons Larger the cations, more is the stabilization of large anions through lattice energy. Oxides are hydrolysed by water to form hydroxides.

Oxides and peroxides Colourless when pure

Superoxides Yellow or orange

Oxidizing agent in inorganic chemistry Superoxide is paramagnetic.

Reason Presence of one unpaired electron in *2p molecular orbital Hydroxides obtained by reaction of oxides with water White crystalline solids Hydroxides of alkali metals are the strongest of all the bases.

Hydroxides dissolve freely in water with evolution of heat.

Halides

Preparation:

By the reaction of aqueous hydrohalic acid (HX) with appropriate oxide, hydroxide or carbonate

Physical properties: Colourless crystalline solids Have high melting points Trend in melting and boiling point:

Fluoride > Chloride > Bromide > Iodide

Soluble in water LiF is less soluble.

Reason: High lattice enthalpy

CsI is less soluble.

Reason: Low hydration enthalpy of the ions

High negative enthalpies of formation (fH ) Trend:

For fluorides fH is less negative down the group. For chlorides, bromides, and iodides fH is more negative down the group. For a given metal

Salts of oxo-acids

An oxo-acid is an acid which contains oxygen has at least one hydrogen atom attached to oxygen contains at least one other atom has the hydroxyl group and the oxo group attached to the same atom

Examples: Carbonic acid (H2CO3), sulphuric acid (H2SO4), nitric acid (HNO3), phosphoric acid (H3PO4)

Preparation:

By the reaction of alkali metals with oxo-acids

Physical properties Soluble in water Thermally stable: Carbonates M2CO3; and in most cases, hydrogen carbonates (MHCO3) are highly thermally stable Exception (I) Li2 CO3 is less stable to heat. Reason: Small size of Li polarization of large stable Li2O and CO2 Exception (II) LiHCO3 does not exist as solid. ion formation of more

Stability of carbonates and hydrogen carbonates increases down the group.

Reason: The electropositive character increases down the group.

Anomalous Properties of Lithium

Reasons for anomalous behaviour of lithium: The Li atom and ion are exceptionally small in size. Li has high polarizing power. [charge to radius ratio (charge/ radius)] Lithium compounds are soluble in organic solvents due to covalent character of lithium compounds because of the above reasons.

Points of difference between lithium and alkali metals Li is harder and has high melting and boiling points. Strongest reducing agent, forms Li2O and Li3N by reacting with air LiCl is deliquescent and crystallises as a hydrate, LiCl. 2H2O. LiHCO3 does not exist as solid. Does not form ethynide with ethyne On heating, lithium nitrate decomposes to oxide while nitrates of other alkali metals decompose to nitrites.

Fluoride and oxide are less soluble in water. Li shows diagonal relationship to Mg. Points of similarities between Li and Mg Both are harder and lighter than the other elements in the respective groups. Both react slowly with water; oxides of both are less soluble in water; hydroxides of both decompose on heating. Both form nitrides (Li3N and Mg3N2) by directly reacting with nitrogen. Both do not form superoxide. On heating, carbonates of both give oxides and CO2; hydrogen carbonates of both do not exist as solid. Chlorides of both (LiCl, MgCl2) are soluble in ethanol, deliquescent, and crystallize as hydrates (LiCl.2H2O, MgCl2.8H2O). Reason for similarities between Li and Mg Similar size

Some Important Compounds of Sodium Washing Soda or Sodium Carbonate (Na2CO3.10H2O)

Preparation Solvay process

Recovering of NH3

Solvay process is not applied to manufacture K2CO3. Reason KHCO3 is soluble in water and hence, cannot be precipitated.

Properties White crystalline solid Easily soluble in water Loses water of crystallization on heating

Carbonate part is hydrolysed by water, resulting in alkaline solution.

Uses In water softening In the manufacture of glass, soap, borax, and caustic soda In industries in the manufacture of paper, paints, and textile In laboratory as a reagent

Sodium Chloride (NaCl)

Preparation

Impurities Sodium sulphate, calcium sulphate, calcium chloride, magnesium chloride

Physical Properties Melts at 1081 K Solubility is 36 g in 100 g of water at 273 K. With the increase in temperature, solubility does not increase. Uses For domestic purpose as common salt or table salt In the preparation of Na2O2, NaOH, and Na2CO3

Caustic Soda or Sodium Hydroxide (NaOH)

Preparation By electrolysis of NaCl in Castner Kellner cell

At anode: At cathode:

Properties White translucent solid Gives alkaline solution by dissolving in water Crystals are deliquescent. At the surface of NaOH solution, Na2CO3 is formed by the reaction with CO2 in the atmosphere. Uses

In petroleum refining process In the manufacture of soap paper, artificial silk, and a number of chemicals In the process of purifying bauxite In textile industries to mercerise cotton fabrics In the preparation of pure fats and oils As a reagent in laboratory

Baking Soda or Sodium Hydrogen Carbonates (NaHCO3)

Called Baking Soda

Reason It decomposes, producing bubbles of CO2 on heating. This is the reason why holes are formed in cakes or pastries and as a result, they are light and fluffy.

Preparation

Uses

As an antiseptic for skin infection For extinguishing fire

Biological Importance of Na and K

Sodium ions take part in the transmission of nerve signals in regulating the water flow across cell membranes in the transportation of sugars and amino acids into cells Potassium ions participate in activating enzymes in cell fluids the oxidation of glucose to produce ATP the transmission of nerve signals

Alkaline Earth Metals

Group 2 elements: Beryllium, magnesium, calcium, strontium, barium and radium.

They are called alkaline earth metals because their oxides and hydroxides are alkaline in nature, and their oxides are found in earths crust.

Electronic Configuration

General outer electronic configuration is ns2 The electronic configurations of the alkaline earth metals are given in the following table: Element Beryllium (Be) Electronic Configuration 1s22s2

Magnesium (Mg) 1s22s22p63s2 Calcium (Ca) Strontium (Sr) Barium (Ba) Radium (Ra) Atomic and ionic radii

1s22s22p63s23p64s2 [Kr] 5s2 [Xe] 6s2 [Rn] 7s2

Smaller than the corresponding alkali metals

Reason: Greater nuclear charge

Increase with the increase in atomic number (i.e., on moving down the group)

Ionisation Enthalpy

Low Decreases on moving down the group. This is because of: Increase in size Increase in the screening of valence electrons from the nuclear charge Higher first ionisation enthalpy than that of the corresponding alkali metals

Reason: Decrease in size

Second ionisation enthalpy is lower than that of the corresponding alkali metals

Hydration enthalpy

Decreases on moving down the group (i.e., with increase in ionic size) Larger hydration enthalpy than that of the corresponding alkali metal ions. This is why compounds of alkaline earth metals are more extensively hydrated than those of alkali metals. Example: NaCl is not hydrated whereas MgCl2 exists as MgCl2.6H2O. KCl does not form hydrate whereas CaCl2 exists as CaCl26H2O.

Physical properties

Silvery white, lustrous and soft (harder than alkali metals) (Exception Beryllium and Magnesium are greyish) Melting and boiling points of these metals are higher than those of the corresponding alkali metals.

Reason: Smaller size than alkali metals

Strongly electropositive in nature. Reason: Low ionisation enthalpies Flame test: Calcium Brick red Strontium Crimson Barium Apple green Mg and Be do not impart colour because the electrons are too strongly bounded to be excited. Good conductors of heat and electricity

Chemical Properties

Less reactive than alkali metals Reactivity increases down the group Reaction with air and water:

Be and Mg are kinetically inert to oxygen and water. Reason formation of oxide film on their surface However, when Mg and powdered Be burn, they give MgO and Mg3N2, and BeO and Be3N2 respectively. Ca, Sr and Ba react readily with air to form oxides and nitrides; also with water (even cold), forming hydroxides Reaction with halogens: At high temperature,

M + X2 MX2 (Halides) (X = F, Cl, Br, I)

(NH4)2BeF4 decomposes to BeF2 on heating BeCl2 is prepared from BeO BeCl2 + CO

BeO + C + Cl2

Reaction with hydrogen: React with hydrogen to form hydrides (Exception Beryllium) Preparation of BeH2 from BeCl2 and LiAlH4

2BeCl2 + LiAlH4 2BeH2 + LiCl + AlCl3

Reaction with acids:

M + 2HCl MCl2 + H2 (M = Alkaline earth metal)

Reducing nature: Strong reducing agent (weaker than corresponding alkali metals) Be is a weaker reducing agent than other alkaline earth metals. Solutions in liquid ammonia:

Dissolve in liquid ammonia to give deep, blue-black solution M + (x + y)NH3 [M(NH3)x]2+ + 2[e(NH3)y] Uses

Beryllium: For making alloys such as CuBe alloys which are used for making high strength springs Metallic Be, for making windows of X-ray tubes Magnesium: For making alloys with Al, Zn, Mn and Sn MgAl alloys are used in the construction of aircraft. Its powder and ribbon forms are used in flash powders and bulbs, incendiary bombs and signals. Milk of magnesia (suspension of (MgOH)2 in water), as an antacid MgCO3, as a component in toothpaste For making armour plates, which are used in thermonuclear reactions Calcium: In the process of extraction of metals from oxides For removing air from vacuum tubes. Reason reacts with oxygen and nitrogen at high temperature Barium: For removing air from vacuum tubes. Reason reacts with oxygen and nitrogen at high temperature Radium: In radiotherapy (e.g., in the treatment of cancer)

General characteristics of compounds of the alkaline earth metals

Compounds of alkaline earth metals are ionic in nature (but less ionic than compounds of corresponding alkali metals). Reason Greater nuclear charge, smaller size Compounds of lighter elements (Be, Mg) are more covalent than those of heavier and large elements (Ca, Sr, Ba).

Oxides and hydroxides

Oxides Burn in oxygen forming metal monoxide (MO) MO has rock salt structure. (Exception BeO) Thermally stable Reason: High enthalpies of formation Ionic in nature (Exception BeO is amphoteric) React with water to form hydroxides, which are sparingly soluble

Hydroxide

Basic in nature (less basic than alkali metal hydroxide)

Exception Be(OH)2 is amphoteric.

Less stable than alkali metal hydroxide

Halides

Ionic in nature (Exception BeX2 is covalent and soluble in organic solvents) Structure of BeCl2 in solid state (chain structure) is

In vapour phase, BeCl2 forms chloro-bridged dimer. At high temperature (1200 K), this dimer undergoes dissociation to form linear monomer.

Tendency to form halide hydrates decreases down the group. Example Salts of oxo-acids

Carbonates Insoluble in water Precipitated by adding sodium or ammonium carbonate Solubility decreases down the group. When heated, decompose to given oxide and CO2 Thermal stability increases down the group. BeCO3 is unstable and hence, kept in the atmosphere of CO2. Sulphate White solids Thermally stable Solubility decreases down the group. BeSO4 and MgSO4 are readily soluble in water. Reason High hydration enthalpy of Be2+ and Mg2+ Nitrates Preparation: By dissolving carbonates in dilute nitric acid Tendency to form hydrates decreases down the group. Reason Increase in size, decrease in hydration enthalpy

Example Mg(NO3)2.6H2O, Ba(NO3)2

When heated, decompose to give oxide

Anomalous Properties of Beryllium

Exceptionally small size of the atom and the cation Forms covalent compounds (due to small size and high ionisation enthalpy) Highest coordination number is four while other members exhibit six.

Reason: Be has four orbitals in its valence shell while other members can use dorbitals Unlike other elements, the oxides and hydroxides of Be are amphoteric in nature.

Diagonal Relationship Between Be and Al

Reason: Same charge/radius ratio Similarities: Like Al, it is not readily attached by acids; (Reason presence of an oxide film on the surface of the metal) Both dissolve in excess of alkali, giving beryllate ion [Be(OH)4]2 and aluminate ion [Al(OH)4]. Like Al2Cl6, BeCl2 has a Cl bridged polymeric structure. Both these compounds are Lewis acids, and are soluble in organic solvents. Both form fluoro complex ions, [BeF4]2, [AlF6]3

Some Important Compounds of Calcium Quick Lime or Calcium Oxide (CaO)

Preparation:

In rotary kiln,

For the completion of the reaction, CO2 is removed as soon as it is produced.

Properties: White amorphous solid Melts at 2870 K Absorbs moisture and CO2 when exposed to atmosphere

Basic oxide combines with acidic oxides on heating

Slaking of lime the process of breaking lump of lime by adding a limited amount of water When slaked with soda, it gives solid soda lime Uses: For manufacturing cement For manufacturing sodium carbonate from caustic soda For manufacturing dye stuffs For purifying sugar It is the cheapest form of alkali

Slaked Lime or Calcium Hydroxide [Ca(OH)2]

Preparation:

By adding water to quick lime

Properties: White amorphous powder Sparingly soluble in water Lime water clear aqueous solution of Ca(OH)2 Milk of lime suspension of slaked lime in water With chlorine, slaked lime gives bleaching powder

On passing carbon dioxide through lime water, it turns milky due to the formation of calcium carbonate (CaCO3)

On passing excess of CO2, calcium carbonate (CaCO3) dissolves, forming calcium hydrogencarbonate

Uses: For the preparation of mortar, a building material Disinfectant in nature, and hence, used in white washing For the manufacture of glass For the preparation bleaching powder For purifying sugar In the tanning industry

Calcium Carbonate (CaCO3)

Naturally Occurs As Limestone, Chalk, Marble Preparation: By passing CO2 through slaked lime On passing excess of CO2, CaCO3 dissolves to form water-soluble calcium hydrogen carbonate.

By adding aqueous solution of sodium carbonate to calcium chloride

Properties: White fluffy powder Insoluble in water Decomposes to CO2 on heating

Reacts with dilute acids to liberate CO2

Uses: As a building material in the form of marble For manufacturing quick lime As a flux with MgCO3 in the extraction of metals such as iron Precipitated CaCO3 for the manufacture of high quality paper As antacid, mild abrasive in toothpaste, in chewing gums, and as filler in cosmetics

Plaster Of Paris or Calcium Sulphate

Hemihydrate of Calcium Sulphate Preparation:

By heating gypsum to 393 K

Above 393 K, water is liberated to form anhydrous calcium sulphate (CaSO4), known as dead burnt plaster.

Property:

On mixing with water, it forms a plastic mass which sets into a hard solid in 5 15 minutes.

Uses: As plaster and as building material In surgical bandages, for setting broken and fractured bones In dentistry For making statues, busts, and in ornamental work

Cement

Also called Portland cement Reason: Resembles the natural limestone extracted in the Isle of Portland, England Composition of cement:

CaO = 50 60% SiO2 = 20 25% Al2O3 = 5 10% MgO = 2 3% Fe2O3 = 1 2% SO3 = 1 2%

For a good-quality cement:

The ratio of SiO2: Al2O3 = 2.5 to 4 The ratio of CaO: (SiO2 + Al2O3 + Fe2O3) = 2

Manufacture of cement: Raw materials limestone and clay On strong heating, clay and lime fuse and react to form Cement clinker. Cement clinker is mixed with 2 3% by weight of gypsum to form cement.

Important ingredients present in Portland cement:

Dicalcium silicate (Ca2SiO4) = 26% Tricalcium silicate (Ca3SiO5) = 51%

Tricalcium aluminate (Ca3Al2O6) = 11%

Setting of cement:

On mixing with water, cement sets to give a hard solid

Reason hydration of the molecules of the constituents and their rearrangement Reason for adding gypsum to slow down the process of setting of the cement; this results in sufficient hardening of the cement Uses:

As a construction material

In concrete and reinforced concrete In plastering In construction of buildings, bridges and dams

Biological Importance of Magnesium and Calcium

Amount of Mg in the human body = 25 g (approx)

Amount of Ca in the human body = 1200 g (approx)

Daily requirement of Ca and Mg in the human body = 200 300 mg Importance of Mg: Required as cofactor by the enzymes that utilise ATP in phosphate transfer Present in chlorophyll Importance of Ca: Bones and teeth contain about 99% body calcium. Plays important roles in neuromuscular function, inter-neuronal transmission, cell membrane integrity, blood coagulation The calcium concentration in plasma is maintained at 100 mgL1 by two hormones Calcitonin Parathyroid hormone

Bone is not an inert and unchanging substance. It is continuously being solubilised and re-deposited to the extent of 400 mg per day in humans.